CA1144562A - Process for the production of urethanes useful in the production of isocyanates - Google Patents
Process for the production of urethanes useful in the production of isocyanatesInfo
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- CA1144562A CA1144562A CA000362772A CA362772A CA1144562A CA 1144562 A CA1144562 A CA 1144562A CA 000362772 A CA000362772 A CA 000362772A CA 362772 A CA362772 A CA 362772A CA 1144562 A CA1144562 A CA 1144562A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
- C07D295/205—Radicals derived from carbonic acid
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D307/91—Dibenzofurans; Hydrogenated dibenzofurans
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
- C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
- C07D333/46—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom
- C07D333/48—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings substituted on the ring sulfur atom by oxygen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Furan Compounds (AREA)
- Heterocyclic Compounds Containing Sulfur Atoms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Pyridine Compounds (AREA)
- External Artificial Organs (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Circuits Of Receivers In General (AREA)
- Polyurethanes Or Polyureas (AREA)
- Peptides Or Proteins (AREA)
Abstract
Mo-2167 LeA 19,838 A PROCESS FOR THE PRODUCTION OF URETHANES
USEFUL IN THE PRODUCTION OF ISOCYANATES
ABSTRACT OF THE DISCLOSURE
The present invention is directed to a process for the production of a urethane. A urea or polyuret, a primary amine and an alcohol are reacted at 120 to 350°C.
The reaction is carried out in the presence of an esterifi-cation catalyst for carboxylic acids. Particularly pre-ferred catalysts include organic and inorganic bases which are inert under the reaction conditions, Lewis acids and transition metal salts or chelates. The ure-thanes produced by this process are particularly useful in the production of organic isocyanates.
LeA 19,838
USEFUL IN THE PRODUCTION OF ISOCYANATES
ABSTRACT OF THE DISCLOSURE
The present invention is directed to a process for the production of a urethane. A urea or polyuret, a primary amine and an alcohol are reacted at 120 to 350°C.
The reaction is carried out in the presence of an esterifi-cation catalyst for carboxylic acids. Particularly pre-ferred catalysts include organic and inorganic bases which are inert under the reaction conditions, Lewis acids and transition metal salts or chelates. The ure-thanes produced by this process are particularly useful in the production of organic isocyanates.
LeA 19,838
Description
~4~62 -1- Mo-2167 LeA 19,838 A PROCESS FOR THE PRODUCTION OF URETHANES
USEFUL IN THE pRoDucTroN/ OF ISOCYANATES
BACKGROUND O~ THE;INVENTION
This invention reIates to an improved process for the production of urethanes by reacting urea or a polyuret with amines and alcohols in the presence of a catalyst.
It is known that urethanes can be formed by react-ing organic isocyanates with alcohols. This reaction is reversible, i.e., urethanes may be thermally split into the isocyanate and the alcohol on which they are based (see, for example, U.S. Patent 2,409,712). Urethanes which can be thermally split into isocyanates are, there-fore, potential starting materials for the production of isocyanates which have been almost universally produced by reacting primary amines with phosgene.
Production of urethanes without phosgene, which urethanes may be subsequently thermally split, is an attractive alternative to the commercially used method for producing isocyanates. One method for producing urethanes without using phosgene is described in U.S.
Patents 2,409,712 and 2,806,051. In this known process, urea is reacted with amines and alcohol. However, this method produces urethanes which contain numerous secondary products in commercially inadequate yields. One of the principal secondary products is the reaction product of alcohol and urea, an N-unsubstituted carbamic acid ester:
o
USEFUL IN THE pRoDucTroN/ OF ISOCYANATES
BACKGROUND O~ THE;INVENTION
This invention reIates to an improved process for the production of urethanes by reacting urea or a polyuret with amines and alcohols in the presence of a catalyst.
It is known that urethanes can be formed by react-ing organic isocyanates with alcohols. This reaction is reversible, i.e., urethanes may be thermally split into the isocyanate and the alcohol on which they are based (see, for example, U.S. Patent 2,409,712). Urethanes which can be thermally split into isocyanates are, there-fore, potential starting materials for the production of isocyanates which have been almost universally produced by reacting primary amines with phosgene.
Production of urethanes without phosgene, which urethanes may be subsequently thermally split, is an attractive alternative to the commercially used method for producing isocyanates. One method for producing urethanes without using phosgene is described in U.S.
Patents 2,409,712 and 2,806,051. In this known process, urea is reacted with amines and alcohol. However, this method produces urethanes which contain numerous secondary products in commercially inadequate yields. One of the principal secondary products is the reaction product of alcohol and urea, an N-unsubstituted carbamic acid ester:
o
2 CO NH2 R O C NH2 + NH3.
SUMMARY OF THE INVENTION
It is an object of the present invention to pro-vide an improved process for producing urethanes byreacting urea with alcohols and amines in such a way that the formation of undesirable secondary products is LeA 19,838 . .
largely avoided. It is a further object of this inven-tion to provide an improved process for producing ure-thanes which are substantially free of undesirable secondary products in commercially si~nificant amounts.
It has now surprisingly been found that these and other objects which will be apparent to those skilled in the art may be achieved by using certain catalysts of the type described in detail below. It has also been found that, in addition to urea, it is also possible to use the 10 higher homologues of urea, i.e., polyurets, in the ure-thane-producing reaction.
Accordingly, the present invention relates to a process for the production of a urethane by reacting a urea or a polyuret with a primary amine and an alcohol 15 at a temperature in the range of from 120 to 350C, characterized in that the reaction is carried out in the presence of an esterification catalyst for carboxylic acids as catalyst.
The process according to the invention is particu-20 larly suitable for the production of urethanes correspond-ing to the following general formula:
,0, _ ln wh1ch n Rl represents an aliphatic hydrocarbon radical con-taining from 1 to 18 carbon atoms which may be substituted, a cycloaliphatic hydrocarbon radical containing from 3 to 18 carbon atoms which may be substituted, an aromatic hydrocarbon radical con-taining from 6 to 15 carbon atoms which may be substituted, an araliphatic hydrocarbon radical containing from 7 to 14 carbon atoms which may be substituted, or a 5- or 6-membered heterocyclic radical which may be substituted and which, LeA 19,838 in addition, may be condensed with a benzene ring, R2 represents an alkyl radical containing from 1 to 20 carbon atoms which may be substituted, a cyclo-alkyl radical containing from 3 to 16 carbon atoms which may be substituted, or an aralkyl radical containing from 7 to 14 carbon atoms which may be substituted, and n is an integer of from 1 to 3.
Where n = 2 or 3, at least 2 carbon atoms should be arranged between the two urethane groups attached to the radical Rl.
Substituents for the aliphatic or cycloaliphatic radicals Rl and R2 include C6-C10 aroxy, Cl-C6 alkoxy, Cl-C6 alkoxy-C2-C4 alkoxy, Cl-C6 acyl, Cl-C6 alkyl 15 mercapto, C6-C10 aryl mercapto, Cl-C12 alkyl carbonyl, bis-(Cl-C8 alkyl)-amino, Cl-C6 acyl amino, nitro, cyano and thiocyano radicals.
Suitable substituents for the aromatic or arali-phatic radicals Rl and R2 include Cl-C12 alkyl, Cl-C12 alkyl sulfonyl, C6-C10 aryl sulfonyl, Cl-C12 alkyl sul-fonic acid ester and sulfonamide radicals.
Preferred products of the process of the present invention are those corresponding to the above general formula in which:
25 Rl represents an aliphatic hydrocarbon radical con-taining from 3 to 18 carbon atoms, a cycloaliphatic hydrocarbon radical containing from 6 to 15 carbon atoms or an aromatic hydrocarbon radical with methylene bridges containing a total of from 6 to 15 carbon atoms which may be methyl, methoxy or chlorine-substituted, R2 represents a Cl-C4 alkoxy- or Cl-C4 alkoxy-C2-C4 alkoxy-substituted or unsubstituted aliphatic hydrocarbon radical containing from 1 to 18 and, more particularly, from 1 to 4 LeA 19,838 .
carbon atoms (the type obtained by removing the hydroxyl group from a monohydric unsubstituted primary or secondary aliphatic alcohol) or a cyclohexyl or a 2-phenyl ethyl radical, and 5 n is the number 1 or 2.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
. . _ .
The present invention is a process for producing urethane in which a urea or a polyuret, a primary amine and an alcohol are reacted in the presence of a catalyst at a temperature of 120 to 350C. Urea or polyurets (such as biurets, triurets or tetraurets) suitable for the practice of the present invention correspond to the formula:
H2N- (CO-NH)m-H
in which m is an integer of from 1 to 4, and mixtures of these compounds.
Primary amines suitable to the practice of the present invention correspond to the formula:
Rl(NH2)n in which Rl and n are as defined above.
Examples of suitable amines include: methyl amine; ethyl amine; propyl amine; isopropyl amine;
butyl amine; i-butyl amine; t-butyl amine; hexyl amine;
dodecyl amine; 2-ethyl hexyl amine; tetradecyl amine;
hexadecyl amine; octadecyl amine; allyl amine; 1,4-diaminobutane; 1,6-diaminohexane; 2,5-dimethyl-2,5-hexane diamine; trimethyl hexamethylene diamine; 2-methoxy ethyl amine; 3-ethoxy propyl amine; 3-butoxy propyl amine; 1,4-butane diol-bis-(3-aminopropyl ether);
SUMMARY OF THE INVENTION
It is an object of the present invention to pro-vide an improved process for producing urethanes byreacting urea with alcohols and amines in such a way that the formation of undesirable secondary products is LeA 19,838 . .
largely avoided. It is a further object of this inven-tion to provide an improved process for producing ure-thanes which are substantially free of undesirable secondary products in commercially si~nificant amounts.
It has now surprisingly been found that these and other objects which will be apparent to those skilled in the art may be achieved by using certain catalysts of the type described in detail below. It has also been found that, in addition to urea, it is also possible to use the 10 higher homologues of urea, i.e., polyurets, in the ure-thane-producing reaction.
Accordingly, the present invention relates to a process for the production of a urethane by reacting a urea or a polyuret with a primary amine and an alcohol 15 at a temperature in the range of from 120 to 350C, characterized in that the reaction is carried out in the presence of an esterification catalyst for carboxylic acids as catalyst.
The process according to the invention is particu-20 larly suitable for the production of urethanes correspond-ing to the following general formula:
,0, _ ln wh1ch n Rl represents an aliphatic hydrocarbon radical con-taining from 1 to 18 carbon atoms which may be substituted, a cycloaliphatic hydrocarbon radical containing from 3 to 18 carbon atoms which may be substituted, an aromatic hydrocarbon radical con-taining from 6 to 15 carbon atoms which may be substituted, an araliphatic hydrocarbon radical containing from 7 to 14 carbon atoms which may be substituted, or a 5- or 6-membered heterocyclic radical which may be substituted and which, LeA 19,838 in addition, may be condensed with a benzene ring, R2 represents an alkyl radical containing from 1 to 20 carbon atoms which may be substituted, a cyclo-alkyl radical containing from 3 to 16 carbon atoms which may be substituted, or an aralkyl radical containing from 7 to 14 carbon atoms which may be substituted, and n is an integer of from 1 to 3.
Where n = 2 or 3, at least 2 carbon atoms should be arranged between the two urethane groups attached to the radical Rl.
Substituents for the aliphatic or cycloaliphatic radicals Rl and R2 include C6-C10 aroxy, Cl-C6 alkoxy, Cl-C6 alkoxy-C2-C4 alkoxy, Cl-C6 acyl, Cl-C6 alkyl 15 mercapto, C6-C10 aryl mercapto, Cl-C12 alkyl carbonyl, bis-(Cl-C8 alkyl)-amino, Cl-C6 acyl amino, nitro, cyano and thiocyano radicals.
Suitable substituents for the aromatic or arali-phatic radicals Rl and R2 include Cl-C12 alkyl, Cl-C12 alkyl sulfonyl, C6-C10 aryl sulfonyl, Cl-C12 alkyl sul-fonic acid ester and sulfonamide radicals.
Preferred products of the process of the present invention are those corresponding to the above general formula in which:
25 Rl represents an aliphatic hydrocarbon radical con-taining from 3 to 18 carbon atoms, a cycloaliphatic hydrocarbon radical containing from 6 to 15 carbon atoms or an aromatic hydrocarbon radical with methylene bridges containing a total of from 6 to 15 carbon atoms which may be methyl, methoxy or chlorine-substituted, R2 represents a Cl-C4 alkoxy- or Cl-C4 alkoxy-C2-C4 alkoxy-substituted or unsubstituted aliphatic hydrocarbon radical containing from 1 to 18 and, more particularly, from 1 to 4 LeA 19,838 .
carbon atoms (the type obtained by removing the hydroxyl group from a monohydric unsubstituted primary or secondary aliphatic alcohol) or a cyclohexyl or a 2-phenyl ethyl radical, and 5 n is the number 1 or 2.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
. . _ .
The present invention is a process for producing urethane in which a urea or a polyuret, a primary amine and an alcohol are reacted in the presence of a catalyst at a temperature of 120 to 350C. Urea or polyurets (such as biurets, triurets or tetraurets) suitable for the practice of the present invention correspond to the formula:
H2N- (CO-NH)m-H
in which m is an integer of from 1 to 4, and mixtures of these compounds.
Primary amines suitable to the practice of the present invention correspond to the formula:
Rl(NH2)n in which Rl and n are as defined above.
Examples of suitable amines include: methyl amine; ethyl amine; propyl amine; isopropyl amine;
butyl amine; i-butyl amine; t-butyl amine; hexyl amine;
dodecyl amine; 2-ethyl hexyl amine; tetradecyl amine;
hexadecyl amine; octadecyl amine; allyl amine; 1,4-diaminobutane; 1,6-diaminohexane; 2,5-dimethyl-2,5-hexane diamine; trimethyl hexamethylene diamine; 2-methoxy ethyl amine; 3-ethoxy propyl amine; 3-butoxy propyl amine; 1,4-butane diol-bis-(3-aminopropyl ether);
3-aminopropanoic acid-2-methyl propyl ester; 6-amino-hexanitrile; lysine ester; l,l-amino-undecanoic acid ester; cyclohexyl amine; cyclohexane nuthane amine;
trimethyl cyclohexyl amine; 2-norbornyl methyl amine;
aniline; o-, m-, ~-chIoroaniline; 2,3-, ~,4-, LeA 19,838 2,5-, 2,6-dichloroaniline; 3,4-dichloroaniline; p-, o-nitroaniline; m-, o-, ~-tolyl aminei 3-trifluoromethyl aniline; 3-chloro-4-methyl aniline; benzyl amine; phenyl cyclohexyl amine; naphthyl amine; 1,4-diaminocyclohexane;
2,4-, 2,6-diamino-1-methyl cyclohexane; 5-amino-1-amino-methyl-1,3,3-trimethyl cyclohexane; 4,4'-diamino-dicyclo-hexyl methane; 4,4'-diamino-3~3'-dimethyl dicyclohexyl methane; 1,3-diaminobenzene; 1,4-diaminobenzene; 2-chloro-1,4-diaminobenzene; 2,4-diaminotoluene; 2,6-diamino-toluene (and mixtures with 2,4-); 2-(N-ethylamino)-4-amino-toluene; 1,3-diamino-2-methylbenzene; 1,3-bis-amino-methylbenzene; 1,3-bis-aminomethyl-4,6-dimethylbenzene;
1,3-diamino-2,6-(4,6)-diethyl-4-methylbenzene; 1,3-diamino-2,4,6-triisopropylbenzene; 1,5-diaminonaphthalene;
2,7-diaminonaphthalene; benzidine; 3,3'-dichloro-benzidine;
trimethyl cyclohexyl amine; 2-norbornyl methyl amine;
aniline; o-, m-, ~-chIoroaniline; 2,3-, ~,4-, LeA 19,838 2,5-, 2,6-dichloroaniline; 3,4-dichloroaniline; p-, o-nitroaniline; m-, o-, ~-tolyl aminei 3-trifluoromethyl aniline; 3-chloro-4-methyl aniline; benzyl amine; phenyl cyclohexyl amine; naphthyl amine; 1,4-diaminocyclohexane;
2,4-, 2,6-diamino-1-methyl cyclohexane; 5-amino-1-amino-methyl-1,3,3-trimethyl cyclohexane; 4,4'-diamino-dicyclo-hexyl methane; 4,4'-diamino-3~3'-dimethyl dicyclohexyl methane; 1,3-diaminobenzene; 1,4-diaminobenzene; 2-chloro-1,4-diaminobenzene; 2,4-diaminotoluene; 2,6-diamino-toluene (and mixtures with 2,4-); 2-(N-ethylamino)-4-amino-toluene; 1,3-diamino-2-methylbenzene; 1,3-bis-amino-methylbenzene; 1,3-bis-aminomethyl-4,6-dimethylbenzene;
1,3-diamino-2,6-(4,6)-diethyl-4-methylbenzene; 1,3-diamino-2,4,6-triisopropylbenzene; 1,5-diaminonaphthalene;
2,7-diaminonaphthalene; benzidine; 3,3'-dichloro-benzidine;
4,4'-diaminodiphenylmethane (and crude products); 3,3'-dichloro-4,4'-diaminodiphenylmethane; 2,2-bis-(4-amino-phenyl)-propane; l,l'-bis-(4-amino-phenyl)-cyclohexane;
1,1'-bis-(4-amino-3-methyl-phenyl)-cyclohexane; 4,4',4"-triaminotriphenylmethane; 4,4'-diaminodiphenylether;
4,4',4"-triaminotriphenylthio-phosphate; ~-methoxy aniline; ~-ethoxy aniline; l-(4-chlorophenoxy)-4-amino-benzene; 2,4-diaminodiphenylether; _-aminobenzoic acid ester; ~-aminobenzoic acid ester; 3,5-diamino-2-methyl-25 diphenylmethane; 3,5-diamino-4-methyl-diphenylmethane (and mixtures); 3,5-diamino-4-methyl dicyclohexyl methane;
3,5-diamino-2-methyl dicyclohexyl methane (and mixtures);
3,5,4'-triamino-4-methyl diphenylmethane; 3,5,4'-tri-amino-2-methyl diphenylmethane; 3,5,2'-triamino-4-methyl 30 diphenylmethane; 3,5,2'-triamino-2-methyl diphenylmethane (and mixtures); 3,5,4'-triamino-4-methyl dicyclohexyl methane; 3,5,4'-triamino-2-methyl dicyclohexyl methane;
3,5,2'-triamino-4-methyl dicyclohexyl methane; 3,5,2'-triamino-2-methyl dicyclohexyl methane (and mixtures);
LeA 19,838 dibenzofuran amine; l-aziridine propane amine; 4-pyridine methane amine; 2-pyridine amine; 1-t3-aminophenyl)-3-methyl-S-pyrazolone; pyrimidine amine; N-aminomorpholine;
2-aminobenzthiazole.
Particularly preferred amines are methyl amine;
propyl amine; isopropyl amine; n-butyl amine; sec.-butyl amine; t-butyl amine; stearyl amine; hexamethylene diamine; cyclohexyl amine; 3,3,5-trimethyl-5-aminomethyl cyclohexyl amine; 4,4'-diaminodicyclohexyl methane;
aniline; ~-chloroaniline; 3,4-dichloroaniline; m-tolyl amine; p-methoxy aniline; 2,4-diaminotoluene; 2,6-di-aminotoluene; 4,4'-diaminodiphenylmethane; 2,4'-diamino-diphenylmethane and commercial mixtures of the above-mentioned diamino-toluenes and diaminodiphenylmethanes.
Alcohols corresponding to the following formula:
R -OH
in which R2 is as defined above are suitable for practice of the present invention.
Examples of suitable alcohols include: methanol;
ethanol; propanol; isopropanol; butanol; isobutanol;
pentanol; isopentanol; hexanol; isohexanol; heptanol;
isoheptanol; octanol; isooctanol; nonanol; isononanol;
decanol; isodecanol; dodecanol; 2-ethyl hexanol; ~-chloro-ethanol; 2-ethyl butanol; hexadecanol; octadecanol; fatty alcohol mixtures; 2-methoxy ethanol; 2-ethoxy ethanol;
2-propoxy ethanol; 2-butoxy ethanol; 2-(2-methoxy ethoxy)-ethanol; 2-(2-ethoxy ethoxy)-ethanol; 2-(2-butoxy ethoxy)-ethanol; cyclopentanol; cyclohexanol; methyl cyclohexanol (and mixtures); cyclohexamethanol; 3,3/5-trimethyl cyclo-hexanol; 4-tert.-butyl cyclohexanol; 2-hydroxydecalin;
borneol; isoborneol; l-(2-hydroxy ethoxy)-4-nitrobenzene;
benzyl alcohol; 2-phenyl ethanol; 2-(methoxy phenoxy) ethanol (mixture); l-phenyl ethanol; 3-phenyl-1-propanol;
LeA 19,838 z 4-methoxy benzyl alcohol; glycol monomethyl ether; glycol monoethyl ether; glycol monoisopropyl ether; gIycol monobutyl ether; glycol monoisobutyl ether; glycol mono-phenol ether; diglycol monoethyl ether; diglycol mono-
1,1'-bis-(4-amino-3-methyl-phenyl)-cyclohexane; 4,4',4"-triaminotriphenylmethane; 4,4'-diaminodiphenylether;
4,4',4"-triaminotriphenylthio-phosphate; ~-methoxy aniline; ~-ethoxy aniline; l-(4-chlorophenoxy)-4-amino-benzene; 2,4-diaminodiphenylether; _-aminobenzoic acid ester; ~-aminobenzoic acid ester; 3,5-diamino-2-methyl-25 diphenylmethane; 3,5-diamino-4-methyl-diphenylmethane (and mixtures); 3,5-diamino-4-methyl dicyclohexyl methane;
3,5-diamino-2-methyl dicyclohexyl methane (and mixtures);
3,5,4'-triamino-4-methyl diphenylmethane; 3,5,4'-tri-amino-2-methyl diphenylmethane; 3,5,2'-triamino-4-methyl 30 diphenylmethane; 3,5,2'-triamino-2-methyl diphenylmethane (and mixtures); 3,5,4'-triamino-4-methyl dicyclohexyl methane; 3,5,4'-triamino-2-methyl dicyclohexyl methane;
3,5,2'-triamino-4-methyl dicyclohexyl methane; 3,5,2'-triamino-2-methyl dicyclohexyl methane (and mixtures);
LeA 19,838 dibenzofuran amine; l-aziridine propane amine; 4-pyridine methane amine; 2-pyridine amine; 1-t3-aminophenyl)-3-methyl-S-pyrazolone; pyrimidine amine; N-aminomorpholine;
2-aminobenzthiazole.
Particularly preferred amines are methyl amine;
propyl amine; isopropyl amine; n-butyl amine; sec.-butyl amine; t-butyl amine; stearyl amine; hexamethylene diamine; cyclohexyl amine; 3,3,5-trimethyl-5-aminomethyl cyclohexyl amine; 4,4'-diaminodicyclohexyl methane;
aniline; ~-chloroaniline; 3,4-dichloroaniline; m-tolyl amine; p-methoxy aniline; 2,4-diaminotoluene; 2,6-di-aminotoluene; 4,4'-diaminodiphenylmethane; 2,4'-diamino-diphenylmethane and commercial mixtures of the above-mentioned diamino-toluenes and diaminodiphenylmethanes.
Alcohols corresponding to the following formula:
R -OH
in which R2 is as defined above are suitable for practice of the present invention.
Examples of suitable alcohols include: methanol;
ethanol; propanol; isopropanol; butanol; isobutanol;
pentanol; isopentanol; hexanol; isohexanol; heptanol;
isoheptanol; octanol; isooctanol; nonanol; isononanol;
decanol; isodecanol; dodecanol; 2-ethyl hexanol; ~-chloro-ethanol; 2-ethyl butanol; hexadecanol; octadecanol; fatty alcohol mixtures; 2-methoxy ethanol; 2-ethoxy ethanol;
2-propoxy ethanol; 2-butoxy ethanol; 2-(2-methoxy ethoxy)-ethanol; 2-(2-ethoxy ethoxy)-ethanol; 2-(2-butoxy ethoxy)-ethanol; cyclopentanol; cyclohexanol; methyl cyclohexanol (and mixtures); cyclohexamethanol; 3,3/5-trimethyl cyclo-hexanol; 4-tert.-butyl cyclohexanol; 2-hydroxydecalin;
borneol; isoborneol; l-(2-hydroxy ethoxy)-4-nitrobenzene;
benzyl alcohol; 2-phenyl ethanol; 2-(methoxy phenoxy) ethanol (mixture); l-phenyl ethanol; 3-phenyl-1-propanol;
LeA 19,838 z 4-methoxy benzyl alcohol; glycol monomethyl ether; glycol monoethyl ether; glycol monoisopropyl ether; gIycol monobutyl ether; glycol monoisobutyl ether; glycol mono-phenol ether; diglycol monoethyl ether; diglycol mono-
5 methyl ether.
Particularly preferred alcohols are: methanol;
ethanol; n-propanol; isopropanol; _-butanol; isobutanol;
cyclohexanol; n-hexanol; 2-ethyl hexanol; ~-phenyl ethanol;
glycol monomethyl ether; glycol monoethyl ether; glycol 10 monobutyl ether; diglycol monomethyl ether; diglycol mono-ethyl ether.
In the practical application of the process according to the invention, the amine is generally used in an amount which is 0.5 to 4 times, preferably 0.8 to 1.5 times and most preferably 0.9 to 1.1 times, the stoi-chiometric amount. The amount of alcohol used is general-ly 1 to 10 times, preferably in 1.1 to 4 times and most preferably 1.1 to 2 times, stoichiometric quantities, based on the carbonyl groups of the urea and/or polyuret.
The process according to the invention is carried out in the presence of catalysts. It has been found that any compounds which have a catalytic effect on the ester-ification reaction of carboxylic acids with alcohols also have an accelerating effect on the reaction according to the present invention. Surprisingly, it has also been found that the effect of using these catalysts is the production of urethanes which have a far lower content of N-unsubstituted urethanes corresponding to the following formula:
than the products of the uncatalyzed reaction.
Catalysts particularly suitable for the process according to the invention are (i) inorganic or organic bases which are inert under the reaction conditions, (ii) Lewis acids and (iii) salts or LeA 19,838 i62 complex compounds, particularly chelates of transition metals.
Examples of suitable catalysts belonging to group (i) include: tertiary amines such as tri-n-5 propyl amine; triethyl amine; triisopentyl amine; diethylbenzyl amine; N,N-dimethyl benzyl amine; hexahydrodimethyl aniline; N-ethyl piperazine; diethyl-(2-methoxy propyl)-amine; 2-(diethyl aminoethyl)-phenyl ether; ethoxyl mor-pholine; N-(2-diethyl aminoethyl)-benzamide; N-(2-diethyl aminoethyl)-propionamide; 1,4-diaza-(2,2,2)-bicyclooctane;
N,N-dimethyl-4-aminopyridine; l-azabicycloheptanes; l-aza-bicyclooctanes; saturated polyheterocyclic amines such as 3-methyl conidine; 1-azabicyclo-(3,2,1)-octane; pyrrolizi-dines and quinuclidines; inorganic bases such as beryllium hydroxide and sodium; potassium, lithium, magnesium, barium or calcium hydroxide; basic alkali salts such as sodium carbonate, sodium sulfide, potassium carbonate or trisodium phosphate; and alkali salts of fatty acids or sulfonic acids.
Suitable catalysts belonging to group (ii) are, for example, Lewis acids such as iron (II) chloride, iron(III) chloride, zinc chloride, tin(II) chloride, tin(IV) chloride, aluminum chloride, zinc cyanide, thallium trichloride, boron trifluoride or bor~n tri-fluoride etherate.
Suitable catalysts belonging to group (iii) include salts of transition metals where they do not already fall within group (ii) and complex compounds, particularly chelates of these metals, such as cobalt, manganese or lead naphthenates, iron oleates or car-bonyls, acetyl acetonates of iron, nickel, cobalt, zinc, lead, aluminum, manganese, magnesium, molybdenum, titanium, thorium, zirconium or vanadium, bis-(dibenzoyl methane)-copper, bis-(ethyl acetoacetate)-LeA 19,838 S~iZ
copper, -iron, coordination compounds of titanium, zir-conium, hafnium, thorium and manganese with ~-diketones, ~-ketoesters and ~-hydroxy aldehydes, dibutyl tin dilaur-ate, dibutyl tin diacetate, di-(2-ethyl hexyl)-tin oxide, dioctyl tin oxide, tin salts of Cl-C20 carboxylic acids such as tin(II) naphthenate, hexoate, palmitate, stearate and dimethyl valerate, acetates, chlorides, sulfates and octoates of divalent or trivalent cobalt, monovalent or divalent copper, zinc or d;valent lead.
Preferred catalysts are zinc chloride, zinc acetate, zinc octoate, zinc oxide~ zinc cyanide, tin(II) chloride, tin(IV) chloride, dibutyl tin dilaurate, cobalt triacetate, cobalt trichloride, cobalt trioctoate, copper~II) acetate, copper(I) chloride, copper(II) sul-fate, lead acetate or lead chloride.
The catalyst is used in a quantity of from 1 ppm to 20% by weight and preferably from 100 ppm to 5% by weight, based on the sum of the urea and/or polyuret, the amine and the alcohol. In practice, every effort should, of course, be made to keep the concentration of the catalyst as low as possible. The optimal catalyst concentration depends upon the starting materials used and upon the activity of the particular catalyst. The appropriate catalyst concentration may be readily deter-mined by methods known to those in the art.
The process according to the invention may becarried out both with or without application of pressure.
The application of pressures in the range from 1 to 80 bars is, however, often appropriate if the reaction temperature lies above the boiling point of one or more of the starting materials. However, even if low boiling alcohols are used it is not absolutely necessary to carry out the process of the invention under pressure since it would also be possible to heat the urea and/or polyuret and the amine to the reaction temperature and to add the low boiling alcohol at a rate which is slow enough to maintain the reaction temperature which lies above the boiling point of the alcohol.
LeA 19,838 The process according to the present invention is gen-erally carried out at te~peratures in the range from 120C to 350C, preferably at temperatures in the range from 130 to 300C and, most preferably, at temperatures in the range from 140 to 250C.
The process according to the present invention may be carried out with or without a solvent. Suitable sol-vents are those which are inert under the process condi-tions and which have a boiling point in the range from 100 to 280C, preferably in the range from 150 to 250C.
Suitable solvents include: n-nonane; n-butyl cyclohexane;
decahydronaphthalene; _-undecane; n-dodecane; n-hexyl cyclohexane; dipentene; l-dodecane; isopropyl benzene;
1,3-diethyl benzene; indene; _-butyl benzene; tetralin;
chlorobenzene; 4-chlorotoluene; 1,2-dichlorobenzene;
2,4-dichlorotoluene; 1,2,4-trichlorobenzene; 2-chloro-4-isopropyl-1-methyl benzene; anisole; cyclohexyl ethyl ether; diethylene glycol dimethyl ether; benzyl methyl ether; 4-methoxy toluene; para-chloroanisole; di-n-hexyl ether; phenyl-n-propyl ketone; benzophenone; acetophe-none; formamide; N,N-dimethyl formamide; N,N-diethyl formamide; N-methyl formamide; dimethyl acetamide; N-methyl pyrrolidone; caprolactam; phenol; substituted phenols; sulfolan; hexamethyl phosphoric acid triamide;
dimethyl sulfoxide; ethylene glycol monomethyl ether acetate; di-_-propyl carbonate; cyclohexyl acetate;
diisobutyl carbonate; diethylene glycol monomethyl ether acetate; diisoamyl carbonate; 2-ethyl pyridine; N,N-dimethyl-2-methyl aniline; N,N-dimethyl aniline; N-methyl-N-ethyl aniline; N,N-dimethyl-2-chloroaniline; N,N-diethyl aniline; quinoline; nitrocyclohexane; nitro-benzene; 2-nitrotoluene; 2,4-dimethyl-1-nitrobenzene;
acetonitrile; N-caprOnitrile; benzonitrile; tolunitrile;
diphenyl ether; tetramethyl urea and phenyl acetonitrile.
It is preferred that polar solvents and mixtures thereof be used with -caprolactam being a particularly suitable solvent.
LeA 19,838 In many cases, for example where a laxge excess of reactant alcohol is used, there is no need to use auxiliary solvents in the production of monourethanes.
To carry out the process according to the invention, the reactants are heated to the reaction temperature, generally over a period of from 1 to 15 hours. Provision must be made to ensure that the ammonia formed during the reaction can escape. The reaction mixture is subsequent-ly treated by techniques known to those in the art such as distillation. When subjected to fractional distilla-tion, the products of the process generally accumulate -as the final fraction or as the distillation residue.
Before the reaction mixtures are treated by distillation, insoluble constituents (for example, insoluble catalysts) may, if necessary, be filtered off. The products of the process may then be thermally split in known manner into the isocyanate and the alcohol on which they are based without further purification.
Having thus described our invention, the following Examples are given by way of illustration. The percent-ages given in these Examples represent percent by weight unless specified otherwise.
EXAMPLES
A packed pressure column (nominal width, 50 mm) having a coil condenser as the head condenser was filled with rings of steel wire mesh cloth (4 mm) to a level of about 1 meter. The sump vessel of the column was a pressure container (nominal capacity, 5 liters; maximum permitted pressure, 64 bars) which was provided with a stirrer and a jacket heating system. Above the head condenser was a valve for removing gases.
1163 g of 2-ethyl hexyl amine, 541 g of urea, 1153 g of methanol and 5.0 g of zinc octoate were intro-duced into the pressure container. After theLeA 19,838 ~!
1~4St~Z
, pressure container and the column were purged with nitro-gen, the mixture was hèated with stirring. By adjusting the valve at the head of the column and the cooling level of the head condenser, the pressure prevailing in the apparatus was regulated in such a way that it was suffi-cient to enable the required reaction temperature to be reached. The mixture was heated to 180C and kept at that temperature for 4.5 hours. The ammonia formed was separated from covolatilized substances by rectification in the column and was removed at the head of the column as substantially pure gaseous ammonia. On completion of the reaction, the mixture was cooled and the apparatus vented again. The reaction solution was analyzed by gas chromatography. A yield of 1500 g (89% of the theore~i-cal) of N-(2-ethyl hexyl)-carbamic acid methyl ester was determined by using an internal standard.
Following the procedure described in Example 1, 1024 g of aniline, 671 g of urea, 1234 g of methanol and 6.2 g of zinc octoate were reacted for 6.5 hours at 200C in the pressure apparatus described in Example 1.
After cooling and venting of the apparatus, the reaction mixture was removed, filtered and freed from most of the excess methanol by distillation at atmospheric pressure.
The mixture was then subjected to fractional distillation under a pressure of 0.2 mbar. 1374 g (82.6~ of the theoretical) of N-phenyl carbamic acid methyl ester melt-ing at 43 to 45C were produced.
Following the procedure described in Example 1, 745 g of aniline, 480 g of urea, 1580 g of ethanol (appro~imately 96%) and 5.9 g of zinc octoate were reacted for 6.5 hours at 200C in the pressure apparatus described in Example 1. After cooling and venting of the apparatus, the reaction mixture was LeA 19,838 removed, filtered and analyzed by liquid chromatography (HPLC). A yield of 1120 g (85% of the theoretical) of N-phenyl carbamic acid ethyl ester was determined.
Following the procedure described in Example 1, 922 g of n-toluidine, 517 g of urea, 1378 g of methanol and 5.8 g of zinc octoate were reacted for 7.0 hours at 190C in the pressure apparatus described in Example 1.
After cooling and venting of the apparatus, the reaction mixture was removed, filtered and analyzed by liquid chromatography (HPLC). A yield of 1210 g (85% of the theoretical) of N-(3-methyl phenyl)-carbamic acid methyl ester was determined.
EXAMPLE S
Following the procedure described in Example 1, 810 g of 3,4-dichloroaniline, 300 g of urea, 927 g of n-butanol, 1200 g of o-dichlorobenzene and 5.0 g of zinc octoate were reacted for 7.0 hours at 200C in the pressure apparatus described in Example 1. After cooling and venting of the apparatus, the reaction mix-ture was removed, filtered and analyzed by liquid chroma-tography (HPLC). A yield of 1140 g (87% of the theoreti-cal) of N-(3,4-dichlorophenyl)-carbamic acid-n-butyl ester was determined.
Following the procedure described in Example 1, 736 g of trans, trans-4,4l-diaminodicyclohexyl methane, 420 g of urea, 1683 g of isopxopanol and 5.7 g of zinc octoate were reacted for 4.5 hours at 190C in the pressure apparatus described in Example 1. After cool-ing and venting of the apparatus, the reaction mixture was removed and analyzed by liquid chromatography (HPLC).
A yield of 1130 g (84% of the theoretical) of 4,4'-bis-(isopropoxycarbonylamino)-dicyclohexyl methane was determined.
LeA 19,838 Following the procedure described in Example 1, 648 g of 2,4-diaminotoluene, 637 g of urea, 153Q g of ethanol (approximately 96~) and 5.3 g of zinc octoate were reacted for 6.0 hours at 200C in the pressure apparatus described in Example 1. After cooling and venting of the apparatus, the reaction mixture was removed, filtered and analyzed by liquid chromatography (HPLC). A yield of 1070 g t76~ of the theoretical) of 2l4-bis-(ethoxycarbonylamino)-toluene was determined.
In a reaction vessel equipped with a reflux con-denser, 1 mol of aniline, 1 mol of urea and 1.4 mols of n-hexanol were rapidly heated to 140C in the presence of 1 g of zinc chloride. The reaction temperature was then generally increased to 200C over a period of 3 hours. After another 2 hours at that temperature, the reaction was complete, i.e., no more ammonia was given off. Analysis of the reaction mixture by liquid chroma-tography showed a yield of 97~, based on urea, of N-phenyl-O-hexyl urethane. The reaction mixture contained less than 1~ of carbamic acid hexyl ester.
744 g of aniline (8 mols) were mixed with 480 g of urea (8 mols), 15 ml of zinc octoate and 1200 g of cyclohexanol (12 mols) and the resulting mixture was introduced into the first three-liter vessel of a three-stage reactor. The three vessels of the reactor were heated to 170C, 200C and 205C. A mixture of 1860 g of aniline (20 mols), 1200 g of urea (20 mols), 25 ml of zinc octoate and 3 kg of cyclohexanol (30 mols), which had been heated to 100C, was pumped into the first vessel over a period of 5 hours. The apparatus was then filled and a mixture LeA 19,838 of 1660 g of aniline (20 mols), 1200 ~ of urea (20 mols), 25 ml of zinc octoate and 3 kg of cyclohexanol (30 mols) was pumped into the reactor over a period of 5 hours.
The final reaction mixture flowed continuously into a thin-layer evaporator where the cyclohexanol was removed in a water jet vacuum. 96~ of the residue left after distillation was N-phenyl-O-cyclohexyl urethane (as determlned by high pressure liquid chromatography = HPLC).
5 ml of zinc octoate were added to 170 g of isophorone diamine (1 mol), 120 g of urea (2 mols) and 250 g of cyclohexanol. The reaction mixture was heated rapidly to 135C to initiate the evolution of ammonia.
The internal temperature was increased to 205C over a period of 6 hours and kept at that level for 3 hours.
After cooling, 51 g of cyclohexanol were distilled off from the residue in a water jet vacuum, leaving a resin which was glass-like and transparent at room temperature.
IR and NR analysis indicated that the resin was almost completely the bis-urethane. 386 g of l-(cyclohexoxy-carbonylamino)-3,3,5-trimethyl-5-(cyclohexoxycarbonyl-amino methyl)-cyclohexane (91% of the theoretical) having a melting point of 159-160~ (from cleaning spirit) were produced.
122 g of 2,4-diaminotoluene (1 mol), 120 g of urea (2 mols) and 250 g of n-hexanol (2.5 mols) are admixed with 1 ml of zinc octoate. The mixture is sub-sequently heated in a reaction yessel equipped with a reflux condenser until a temperature of the mixture of 180C is reached. Subsequently 160 ml of n-hexanol are added dropwise so that the reaction temperature of 180C can be maintained. After a total reaction time of 17 hours the content of the reaction LeA 19,838 i6Z
mixture is determined by HPLC and found to correspond to 93% of the theoretical. Excess hexanol is then distilled off and the residue is recrystallized from isopropanol/
cleaning spirit. 308 g of 2,4-bis-(n-hexoxycarbonyl-amino)-toluene (-81% of theoretical yield) having a melt-ing point of from 82-83C are obtained.
EXAMPLE lla Example 11 is repeated with the only difference that O.S mol of the 2,4-diaminotoluene are replaced by 0.5 mol of 2,6-diaminotoluene. The yield of the corres-ponding urethanes was found to correspond to 91% of the theoretical yield.
324 g of 3,4-dichloroaniline (2 mols), 120 g of urea (2 mols), 300 g of cyclohexanol (3 mols) and 1 ml of zinc octoate are heated for 13 hours to reflux tempera-ture. The reaction temperature rises to 205C. After removal of excess cyclohexanol by distillation 655 g of residue are obtained which contains the urethane in an amount which corresponds to 90~ of the theoretical yield (HPLC analysis).
After recrystallization from cleaning spirit 470 g N-(3,4-dichlorophenyl)-cyclohexyl urethane (82~ of the theoretical yield) having a melting point of from 116 to 118C are obtained.
200 g of caprolactam were added to 183 g of 3-aminodibenzofuran (1 mol), 60 g of urea (1 mol), 150 g of cyclohexanol (1.5 mols) and 2 ml of zinc acetate.
The resulting mixture was heated rapidly to 200C caus-ing evolution of ammonia. After 5 hours at that tempera-ture, the reaction was complete and the excess cyclo-hexanol was distilled off. The residue was introduced into water, the insoluble fraction was filtered off, dried and recrystallized from cleaning spirit. 236 g of N-(3-dibenzofuranyl)-LeA 19,838 -16a-_-cyclohexyl urethane (76% of the theoretical) having a melting point of 13I-133C were.produced.
113 g of 4-morpholine amine (90%, 1 mol), 60 g of urea (1 mol), 150 g of cyclohexanol (1 mol) and 2 g of zinc acetate were combined and heated to 135C, initiating the evolution of ammonia. The temperature LeA 19,838 11445~2 was increased s~owly to 190~C and kept at that level for 4 hours. The excess cyclohexanol (52 g~ was removed in a water jet vacuum in a rotary evaporator and the residue was recrystallized from cleaning spirit. 166 g of N-(4-morpholinyl)-cyclohexyl urethane (73% of the theoretical) having a melting point of 150-152C were produced.
157 g of 3-aminosuifolane ~86%, 1 mol), 60 g of urea (1 mol), 150 g of cyclohexanol (1.5 mols) and 2 ml of zinc octoate were mixed in a 500 ml three-necked flask equipped with a stirrer, thermometer and reflux condenser. The resulting mixture was heated over a period of 4 hours to 190C with evolution OL
ammonia. After another 3 hours at 193C, the reaction was complete. 45 g of cyclohexanol were removed in a water jet vacuum and the residue was recrystallized from ethyl acetate. 241 g of N-(3-sulfolanyl)-cyclo-hexyl urethane (92% of the theoretical) having a melting point of 139C were produced.
324 g of benzyl alcohol (3 mols), 205 ~ of aniline (2.2 mols) and 120 g of urea (2 mols) were mixed in a one-liter flask. 1 g of zlnc octoate and 2 g of dibutyl tin dilaurate were added to the \~ resulting mixture which wa~ then rapidly heated to 135C, initiating t~e evolution of ammonia. The internal temperature was increased to 200C over a period of 3 hours and kept between 195C and 205C
for another 5 hours. On completion of the reaction, excess benzyl alcohol and aniline were distilled off in a water jet vacuum. The residue was fractionated in a high vacuum. 336 g of N-phenyl benzyl urethane (74~ of the theoretical) having a boiling point of 142-145C at 0.13 mbar were produced.
LeA 19,838 Z
2 g of zinc cyanide were added to 94 g of 2-aminopyridine (1 mol), 60 g of urea (1 mol), 150 g of cyclohexanol (1.5 mols). The resulting mixture was 5 heated to 135C, initiating the evolution of ammonia.
The temperature was increased to 200C over a period of 4 hours and left at that level for another 2 hours. 55 g of cyclohexanol were then distilled off in a water jet vacuum and the residue was recrystallized from cleaning spirit. 170 g of N-(2-pyridyl)-cyclohexyl urethane (77% of the theoretical) having a melting point of 145-147C were produced.
-2.5 ml of zinc octaate were added to 306 g of n-hexanol (3 mols), 205 g of aniline (2.2 mols) and 120 g of urea t2 mols). The resulting mixture was heated over a period of 5 hours to 200C with evolution of ammonia.
After another 3 hours at that temperature, the reaction was complete and excess cyclohexanol and aniline were removed in a water jet vacuum. The quantity of the reac-tion product was determined by HPLC to be 345 g of N-phenyl-_-hexyl urethane (87~ of the theoretical). The product crystals had a melting point of 42-43C (from cleaning spirit).
3 g of cobalt acetate were added to 127.5 g of ~-chloroaniline (1 mol), 60 g of urea (1 mol) and 140 g of cyclohexanol (1.4 mols). The reaction mixture was heated to 150C, initiating the evolution of ammonia.
The internal temperature was increased to 200C and kept at that level for 5 hours. Excess cyclohexanol was then removed by distillation and the residue was recrystal-lized from xylene. 218 g of N-t_-chlorophenyl)-cyclo-hexyl urethane (86% of the LeA 19,838 1~44562 theoretical) having a melting point of 115-116C
were produced.
E~LE 20 116 g of 1,6-diaminohexane (1 mol) r 120 g of urea (2 mols), 250 g of cyclohexanol (2.5 mols), 100 g of caprolactam and 3 ml of zinc octoate were heated to 140C, initiating the elimination of ammonia. The internal temperature was increased to 200C over a period of 4 hours and the reaction mixture was heated for another 3 hours at 205C. Cyclohexanol was then removed in a water jet vacuum and caprolactam was removed in a high vacuum. The residue wzs identified and determined by IR, NR and HPLC. 316 g of l,6-bis-(cyclohexoxycarbonylamino)-hexane (86% of the theoretical) were produced. A sample was recrystallized from cleaning spirit. The recrystallized sample had a melting point of 110-111C.
250 g of cyclohexanol ~2.5 mols), 120 g of urea (2 mols) and 3 ml of zinc octoate were heated to 140C and 118 g of propylamine (2 mols) were added slowly, dropwise, at that temperature. On completion of the addition, the internal temperature was increased to 200C and the xeaction mixture was sitrred for 1 hour at that temperature. The unreacted cyclohexanol was distilled off in a water jet vacuum and the residue was distilled in an oil pump vacuum. 292 g ~79% of the theoretical) of N-(n-propyl)-O-cyclohexyl urethane ~identified by HPLC) were produced.
198 g of 4,4'-diaminodiphenylmethane (1 mol), 120 g of urea (2 mols), 400 ml of cycloheYanol (4 mols), 3 ml of zinc octoate and 452 g of caprolactam were mixed and the resulting mixture was heated over a period of 3 hours to 210~C. After heating for 4 hours at that temperature, the evolution of ammonia LeA 19,838 ~144S62 .
was complete. The reaction mixture which had a temperature of 40C was then stirred into ice water, mixed with ethyl acetate and separated. The ethyi acetate phase was repeatedly washed with ice water, dried over sodium sulfate and concentrated. The residue was recrystallized from xylene. 415 g of 4,4'-bis-(cyclohexoxycarbonylamino)-diphenylmethane ~86% of the theoretical) having a melting point of 144C were produced.
258.3 g (2.1 mols) of 4-methoxy aniline, 120 g t2 mols) of urea and 330.4 g (2.8 mols) of glycol monobutyl ether were heated under reflux for 2 hours with 3 g of cobalt acetate. After the temperature had reached 200C, the reaction mixture was kept at that temperature for another 8 hours. After removal of the excess glycol monobutyl ether, the reaction product was dissolved in 500 ml of toluene, filtered off under suction from the insoluble residue, extracted with 1 N HCl and worked up, leaving a chromato-graphically (thin-layer chromatography) pure oil which was identified by spectroscopy as N-(4-methoxy phenyl)-O-~-n-butoxy ethyl urethane. The yield amounted to 87% of the theoretical.
_ 204.6 g (2.2 mols) of aniline, 120 g (2 mols) of urea and 354 g (3 mols) of ethylene glycol mono-butyl ether were heated under reflux with 0.8 of dibutyl tin dilaurate. After 2 hours, the temperature reached 200C and was kept at that level for another 9 hours. The solution was concentrated and the residue was treated with hot ligroin. The solution was then filtered off undér suction from the insoluble diphenyl urea and the ligroin was distilled off again, leaving a noncrystallizing oil, of which more than 95% was found by nuclear-resonance spectroscopy to LeA 19,838 consist of N-phenyl-O-~-n-butoxy ethyl urethar.e. The yield amounted to more than 90% of the tneoretical.
-204.6g(2.2 mols) of aniline, 120 g (2 mols) of urea and 366 g (3 mols) of ~-phenyl ethanol were heated with 3 g of thallium chloride. The reflux temperature rose over a period of 1.5 hours to 200C.
When the evolution of ammonia ceased, the reaction mixture was kept at 200C for another 10 hours. The yield of N-phenyl-O-~-phenyl ethyl urethane was determined by high pressure liquid chroma.ography and amounted to more than 90% of the theoretical.
. .
235.4 g (2.2 mols) of 3-methyl aniline, 120 g (2 mols) of urea and 390 g (3 mols) of 2-ethyl-1-hexanol were heated under reflux for 3 hours with 0.8 g of triethylenediamine, ammonia being given off. The temperature rose to 200C. After another 7 hours at 200C, the reaction mixture was concentrated ln vacuo.
The hot residue was mixed with 500 ml of cleaning spirit and the resulting solution filtered off under suction from the insoluble fraction. 0-2-ethyl hexyl-(l)-N-phenyl urethane was isolated from the filtrate by distillation (0.2 mbar, 147-150C) in a yield which was 85% of the theoretical yield.
354 g (1.2 mols) of ethylene glycol monobutyl ether, 120 g ~2 mols) of urea and 185.4 g (1.2 mols) of 3-aminotetramethylene sulfone were heated under reflux with 0.8 g of zinc octoate. After 3 hours, the temperature had reached 200C and was kept at that level for another 8 hours. The recyclable starting and secondary products were removed by dis-tillation at 0.6 mbar (temperature: up to 115C).
According to analysis by infrared and nuclear-resonance spectroscopy, the residue was N-(3-perhydrothiophenyl-LeA 19,838 l,l-dioxo)-O-~-_-butoxy ethyl urethane. The yield was 85% of the theoretical yield.
EXAMP~E 28 198 g (2 mols) of cyclohexyl amine, 132 g (2.2 mols) of urea and 244 g (2 mols) of ~-phenyl ethanol were heated under reflux to 200C with 0.2 g of zinc octoate. Another 122 g (1 mol) of ~-phenyl ethanol were then added and the reaction mixture was kept at 200C for 4 hours. 79% of the theoretical yield of N-cyclohexyl-O-~-phenyl ethyl urethane melting at 86 to 88C (cleaning spirit) were produced.
103 g (1 mol) of biuret, 186 g (2 mols) of aniline, 300 g (3 mols) of cyclohexanol and 0.5 g of zinc octoate were heated under reflux for 4 hours, the temperature reaching 200C. The reaction mixture was then kept at 200C for another 4 hours. The yield of O-cyclohexyl-N-phenyl urethane was determined by high pressure liquid chromatography to be 92% of the theoretical yield.
The reaction was repeated without the catalyst.
The reaction mixture was kept at 200C for a period of 20 hours. The yield of O-cyclohexyl-N-phenyl urethane was determined by high pressure liquid chromatography to be 60% of the theoretical yield.
272 g (2 mols) of 4-nitroaniline, 120 g (2 mols) of urea, 300 g (3 mols) of cyclohexanol and 0.8 g of zinc octoate were heated under reflux. After the temperature had reached 2Q0C, it was kept at that level for 7 hours.
327 g (62% of the theoretical yield) of O-cyclohexyl-n-4-nitrophenyl urethane melting at 117C were obtained by recrystallization from ethanol/water.
3-nitroaniline was reacted by the method des-cribed above, giving 370 g (70% of the theoretical) LeA 19,838 ``` 11~4S6Z
yield) of O-cyclohexyl-N-3-nitrophenyl urethane melting at 115C.
2-nitroaniline was reacted by the method described above, giving 208 g (43% of the theoretical yield) of O-cyclohexyl-N-2-nitrophenyl urethane melting at 104C.
204.6 g (2.2 mols) of aniline, 132 g (2.2 mols) of urea, 300 g (3 mols) of cyclohexanol, 0.8 g of zinc octoate and 0.2 g of tin octoate were heated under reflux. The reaction temperature was increased from 150C to 200C over a period of 2 hours. The tempera-ture was kept at 200C for another 8 hours. During the reaction, ethanol was continuously passed through the solution at a rate of 50 ml/hour and removed overhead. The urethane yields were determined by high pressure liquid chromatography. 95.4~ of the theoretical yield of O-cyclohexyl-N-phenyl urethane and 3.7% of the theoretical yield of O-ethyl-N-phenyl urethane were formed.
204.6 g (2.2 mols) of aniline, 120 g (2 mols~
of urea, 300 g (3 mols) of cyclohexanol and 0.6 g of zinc octoate were heated under reflux. The reaction temperature was raised from 150C to 200C over a period of 2 hours. When the evolution of a~monia ceased, the reaction mixture was kept at 200C with the course of the reaction being continuously monitored by high pressure li~uid chromatography. After 6 hours, the yield of O-cyclohexyl-N-phenyl urethane amounted to 97.9~ of the theoretical yield. After recry~stal-lization , 416 g (95~ of the theoretical yield) of the urethane ~Mp 80C) were obtained.
EX~MPLE 33 Phenyl carbamic acid butyl ester was produced by heating a mixture of 60.06 g (l mol) of urea, LeA 19,838 102.4 g (1.1 mol) of aniline and 0,5 resp. 2 9 Ot the catalysts mentioned below to 150C in a 500 ml three necked flask equipped with a stirrer, internal thermometer and reflux condenser. 150-200 ml of butanol were added dropwise over a period of 6 hours with stirring and further heating. The rate of addition was selected so that a reaction temperature of 175C was maintaired.
The conversion was estimated through the evolution of ammonia. The reaction mixture was worked up b,y dis-tillation of the carbamate.
The yield of N-phenyl-O-butyl urethane (HPLC Oc the reaction mixture) for catalyzed and uncatalyzed reactions were as follows:
Catalyst Yield None 140.6 g 72.8% (theoretical) 2 g of CU(oAc)2-H2o 161.0 g 83.4~ (theoretical) 0.5 g of Octasoli~en-Zn 179.2 g 92.9~ (theoretical) 186 g of aniline (2 mols), 120 g of urea (2 mols), 300 ml of cyclohexanol (3 mols) and 3 g of catalyst were boiled unaer reflux for 9 hours. The e~cess cyclo-hexanol was removed in a water jet vacuum and the yield of N-phen~-l-O-cyclohexyl urethane was determi,ned by HPLC.
The following Table illustrates the effect of the various catalysts upon the reaction described above. A noncatalyzed batch was run for purposes of comparison. Thé yields are given in terms of mol percent.
LeA 19,838 Catalyst Yield Zn-octoate 97 TlCl 95 ZnCl2 95 ZnSO4 94 5 2 94.4 Dabco 94 Co-naphthenate 94 DBU 92.5 TiCl4 92 Zn-dust 92 2-hydroxypyridine 92 K-acetate 92 BiCl3 92 BF3-etherate 91.5 Dibenzylamine 91 AlCl3 91 Zn-acetate 91 Fe-acetyl acetonate 90.5 Cu-acetate 90 Na-methylate 90 Zn~CN)2 90 ZnO 90 Sn-octoate 89.5 None 81 LeA 19,838 11~4S6Z
Example 35 A 3 l reaction vessel is equipped with a stirrer~ermometar~
reflux condenser, heatable ethanol inlet tube and a gas outlet tube. 814 g of urea, 1302 9 of aniline and 7 g of dibutyltin-oxide are heated within 1 hour to 170C.
Subsequently ethanol vapours are pumped into the reaction mixture the amount of ethanol was 400 g/h at the besinninG
of the introduction of the vapours and is continuously reduced so that a reaction temperature of 170C can be maintained. According to HPLC analysis N-phenyl-carbamic-acid ethyl ester is formed in an amount of 1779 9 (77 %of the theoretical yield) after 10 hours and in an amount of 1917 9 (83 % of the theoretical yield~ after 23 hours.
F;nally 1746 9 (76 % of the theoretical yield) of N-phenyl-carbamic acid ethyl ester can be obtained by distillatio-at 110C/0,13 mbar containing only 1,8 % by weight of N,N'-diphenylurea and 30 ppm of zinc. The distilla'ion residue (379 9) contains 21 % by weight of N-phenylcarbamic acid ethyl ester, 61 % by weight of N,N'-diphenyl urea and Z 0,85 ~ by weight of zinc.
~ ~ LeA 19 838 ~ 4S62 A 0.5 1 reaction vessel is equipped with a stirrer, dropping funnel and a reflux condenser with a gas outlet tube. The inlet tube of the dropping funnel immerses into the reaction mixture. 60.1 g of urea, 93.1 g of aniline and 0.5 g of dimethyl-tin-dichloride are heated in the reaction vessel under stirring and nitrogen to 170C Subsequently 73 g of ethanol are added at such a rate that the reaction temperature can be maintained between 170 and 175C After 10 hours the reaction is stopped by cooling to room temperature. According to HPLC analysis 140.3 g (85% of the theoretical yield) of N-phenylcarbamic acid ethyl ester have been formed.
144 g of urea, 480 g of diethylene glycol mono-methyl ether and 0.8 g of zinc octoate are heated for 1 hour to reflux temperature. At 200C 198 g of 4,4'-diamino-diphenylmethane and so much diethylene glycol dimethyl ether are added dropwise at such a rate that the temperature of the reaction mixture does not rise above 200C.
After 9 hours 4,4'-bis-[2~2'-methoxyethoxy)-ethoxy-carbonylamino]-diphenylmethane is found by HPLC
analysis in an amount which corresponds to 90% of the theoretical yield.
LeA 19,838
Particularly preferred alcohols are: methanol;
ethanol; n-propanol; isopropanol; _-butanol; isobutanol;
cyclohexanol; n-hexanol; 2-ethyl hexanol; ~-phenyl ethanol;
glycol monomethyl ether; glycol monoethyl ether; glycol 10 monobutyl ether; diglycol monomethyl ether; diglycol mono-ethyl ether.
In the practical application of the process according to the invention, the amine is generally used in an amount which is 0.5 to 4 times, preferably 0.8 to 1.5 times and most preferably 0.9 to 1.1 times, the stoi-chiometric amount. The amount of alcohol used is general-ly 1 to 10 times, preferably in 1.1 to 4 times and most preferably 1.1 to 2 times, stoichiometric quantities, based on the carbonyl groups of the urea and/or polyuret.
The process according to the invention is carried out in the presence of catalysts. It has been found that any compounds which have a catalytic effect on the ester-ification reaction of carboxylic acids with alcohols also have an accelerating effect on the reaction according to the present invention. Surprisingly, it has also been found that the effect of using these catalysts is the production of urethanes which have a far lower content of N-unsubstituted urethanes corresponding to the following formula:
than the products of the uncatalyzed reaction.
Catalysts particularly suitable for the process according to the invention are (i) inorganic or organic bases which are inert under the reaction conditions, (ii) Lewis acids and (iii) salts or LeA 19,838 i62 complex compounds, particularly chelates of transition metals.
Examples of suitable catalysts belonging to group (i) include: tertiary amines such as tri-n-5 propyl amine; triethyl amine; triisopentyl amine; diethylbenzyl amine; N,N-dimethyl benzyl amine; hexahydrodimethyl aniline; N-ethyl piperazine; diethyl-(2-methoxy propyl)-amine; 2-(diethyl aminoethyl)-phenyl ether; ethoxyl mor-pholine; N-(2-diethyl aminoethyl)-benzamide; N-(2-diethyl aminoethyl)-propionamide; 1,4-diaza-(2,2,2)-bicyclooctane;
N,N-dimethyl-4-aminopyridine; l-azabicycloheptanes; l-aza-bicyclooctanes; saturated polyheterocyclic amines such as 3-methyl conidine; 1-azabicyclo-(3,2,1)-octane; pyrrolizi-dines and quinuclidines; inorganic bases such as beryllium hydroxide and sodium; potassium, lithium, magnesium, barium or calcium hydroxide; basic alkali salts such as sodium carbonate, sodium sulfide, potassium carbonate or trisodium phosphate; and alkali salts of fatty acids or sulfonic acids.
Suitable catalysts belonging to group (ii) are, for example, Lewis acids such as iron (II) chloride, iron(III) chloride, zinc chloride, tin(II) chloride, tin(IV) chloride, aluminum chloride, zinc cyanide, thallium trichloride, boron trifluoride or bor~n tri-fluoride etherate.
Suitable catalysts belonging to group (iii) include salts of transition metals where they do not already fall within group (ii) and complex compounds, particularly chelates of these metals, such as cobalt, manganese or lead naphthenates, iron oleates or car-bonyls, acetyl acetonates of iron, nickel, cobalt, zinc, lead, aluminum, manganese, magnesium, molybdenum, titanium, thorium, zirconium or vanadium, bis-(dibenzoyl methane)-copper, bis-(ethyl acetoacetate)-LeA 19,838 S~iZ
copper, -iron, coordination compounds of titanium, zir-conium, hafnium, thorium and manganese with ~-diketones, ~-ketoesters and ~-hydroxy aldehydes, dibutyl tin dilaur-ate, dibutyl tin diacetate, di-(2-ethyl hexyl)-tin oxide, dioctyl tin oxide, tin salts of Cl-C20 carboxylic acids such as tin(II) naphthenate, hexoate, palmitate, stearate and dimethyl valerate, acetates, chlorides, sulfates and octoates of divalent or trivalent cobalt, monovalent or divalent copper, zinc or d;valent lead.
Preferred catalysts are zinc chloride, zinc acetate, zinc octoate, zinc oxide~ zinc cyanide, tin(II) chloride, tin(IV) chloride, dibutyl tin dilaurate, cobalt triacetate, cobalt trichloride, cobalt trioctoate, copper~II) acetate, copper(I) chloride, copper(II) sul-fate, lead acetate or lead chloride.
The catalyst is used in a quantity of from 1 ppm to 20% by weight and preferably from 100 ppm to 5% by weight, based on the sum of the urea and/or polyuret, the amine and the alcohol. In practice, every effort should, of course, be made to keep the concentration of the catalyst as low as possible. The optimal catalyst concentration depends upon the starting materials used and upon the activity of the particular catalyst. The appropriate catalyst concentration may be readily deter-mined by methods known to those in the art.
The process according to the invention may becarried out both with or without application of pressure.
The application of pressures in the range from 1 to 80 bars is, however, often appropriate if the reaction temperature lies above the boiling point of one or more of the starting materials. However, even if low boiling alcohols are used it is not absolutely necessary to carry out the process of the invention under pressure since it would also be possible to heat the urea and/or polyuret and the amine to the reaction temperature and to add the low boiling alcohol at a rate which is slow enough to maintain the reaction temperature which lies above the boiling point of the alcohol.
LeA 19,838 The process according to the present invention is gen-erally carried out at te~peratures in the range from 120C to 350C, preferably at temperatures in the range from 130 to 300C and, most preferably, at temperatures in the range from 140 to 250C.
The process according to the present invention may be carried out with or without a solvent. Suitable sol-vents are those which are inert under the process condi-tions and which have a boiling point in the range from 100 to 280C, preferably in the range from 150 to 250C.
Suitable solvents include: n-nonane; n-butyl cyclohexane;
decahydronaphthalene; _-undecane; n-dodecane; n-hexyl cyclohexane; dipentene; l-dodecane; isopropyl benzene;
1,3-diethyl benzene; indene; _-butyl benzene; tetralin;
chlorobenzene; 4-chlorotoluene; 1,2-dichlorobenzene;
2,4-dichlorotoluene; 1,2,4-trichlorobenzene; 2-chloro-4-isopropyl-1-methyl benzene; anisole; cyclohexyl ethyl ether; diethylene glycol dimethyl ether; benzyl methyl ether; 4-methoxy toluene; para-chloroanisole; di-n-hexyl ether; phenyl-n-propyl ketone; benzophenone; acetophe-none; formamide; N,N-dimethyl formamide; N,N-diethyl formamide; N-methyl formamide; dimethyl acetamide; N-methyl pyrrolidone; caprolactam; phenol; substituted phenols; sulfolan; hexamethyl phosphoric acid triamide;
dimethyl sulfoxide; ethylene glycol monomethyl ether acetate; di-_-propyl carbonate; cyclohexyl acetate;
diisobutyl carbonate; diethylene glycol monomethyl ether acetate; diisoamyl carbonate; 2-ethyl pyridine; N,N-dimethyl-2-methyl aniline; N,N-dimethyl aniline; N-methyl-N-ethyl aniline; N,N-dimethyl-2-chloroaniline; N,N-diethyl aniline; quinoline; nitrocyclohexane; nitro-benzene; 2-nitrotoluene; 2,4-dimethyl-1-nitrobenzene;
acetonitrile; N-caprOnitrile; benzonitrile; tolunitrile;
diphenyl ether; tetramethyl urea and phenyl acetonitrile.
It is preferred that polar solvents and mixtures thereof be used with -caprolactam being a particularly suitable solvent.
LeA 19,838 In many cases, for example where a laxge excess of reactant alcohol is used, there is no need to use auxiliary solvents in the production of monourethanes.
To carry out the process according to the invention, the reactants are heated to the reaction temperature, generally over a period of from 1 to 15 hours. Provision must be made to ensure that the ammonia formed during the reaction can escape. The reaction mixture is subsequent-ly treated by techniques known to those in the art such as distillation. When subjected to fractional distilla-tion, the products of the process generally accumulate -as the final fraction or as the distillation residue.
Before the reaction mixtures are treated by distillation, insoluble constituents (for example, insoluble catalysts) may, if necessary, be filtered off. The products of the process may then be thermally split in known manner into the isocyanate and the alcohol on which they are based without further purification.
Having thus described our invention, the following Examples are given by way of illustration. The percent-ages given in these Examples represent percent by weight unless specified otherwise.
EXAMPLES
A packed pressure column (nominal width, 50 mm) having a coil condenser as the head condenser was filled with rings of steel wire mesh cloth (4 mm) to a level of about 1 meter. The sump vessel of the column was a pressure container (nominal capacity, 5 liters; maximum permitted pressure, 64 bars) which was provided with a stirrer and a jacket heating system. Above the head condenser was a valve for removing gases.
1163 g of 2-ethyl hexyl amine, 541 g of urea, 1153 g of methanol and 5.0 g of zinc octoate were intro-duced into the pressure container. After theLeA 19,838 ~!
1~4St~Z
, pressure container and the column were purged with nitro-gen, the mixture was hèated with stirring. By adjusting the valve at the head of the column and the cooling level of the head condenser, the pressure prevailing in the apparatus was regulated in such a way that it was suffi-cient to enable the required reaction temperature to be reached. The mixture was heated to 180C and kept at that temperature for 4.5 hours. The ammonia formed was separated from covolatilized substances by rectification in the column and was removed at the head of the column as substantially pure gaseous ammonia. On completion of the reaction, the mixture was cooled and the apparatus vented again. The reaction solution was analyzed by gas chromatography. A yield of 1500 g (89% of the theore~i-cal) of N-(2-ethyl hexyl)-carbamic acid methyl ester was determined by using an internal standard.
Following the procedure described in Example 1, 1024 g of aniline, 671 g of urea, 1234 g of methanol and 6.2 g of zinc octoate were reacted for 6.5 hours at 200C in the pressure apparatus described in Example 1.
After cooling and venting of the apparatus, the reaction mixture was removed, filtered and freed from most of the excess methanol by distillation at atmospheric pressure.
The mixture was then subjected to fractional distillation under a pressure of 0.2 mbar. 1374 g (82.6~ of the theoretical) of N-phenyl carbamic acid methyl ester melt-ing at 43 to 45C were produced.
Following the procedure described in Example 1, 745 g of aniline, 480 g of urea, 1580 g of ethanol (appro~imately 96%) and 5.9 g of zinc octoate were reacted for 6.5 hours at 200C in the pressure apparatus described in Example 1. After cooling and venting of the apparatus, the reaction mixture was LeA 19,838 removed, filtered and analyzed by liquid chromatography (HPLC). A yield of 1120 g (85% of the theoretical) of N-phenyl carbamic acid ethyl ester was determined.
Following the procedure described in Example 1, 922 g of n-toluidine, 517 g of urea, 1378 g of methanol and 5.8 g of zinc octoate were reacted for 7.0 hours at 190C in the pressure apparatus described in Example 1.
After cooling and venting of the apparatus, the reaction mixture was removed, filtered and analyzed by liquid chromatography (HPLC). A yield of 1210 g (85% of the theoretical) of N-(3-methyl phenyl)-carbamic acid methyl ester was determined.
EXAMPLE S
Following the procedure described in Example 1, 810 g of 3,4-dichloroaniline, 300 g of urea, 927 g of n-butanol, 1200 g of o-dichlorobenzene and 5.0 g of zinc octoate were reacted for 7.0 hours at 200C in the pressure apparatus described in Example 1. After cooling and venting of the apparatus, the reaction mix-ture was removed, filtered and analyzed by liquid chroma-tography (HPLC). A yield of 1140 g (87% of the theoreti-cal) of N-(3,4-dichlorophenyl)-carbamic acid-n-butyl ester was determined.
Following the procedure described in Example 1, 736 g of trans, trans-4,4l-diaminodicyclohexyl methane, 420 g of urea, 1683 g of isopxopanol and 5.7 g of zinc octoate were reacted for 4.5 hours at 190C in the pressure apparatus described in Example 1. After cool-ing and venting of the apparatus, the reaction mixture was removed and analyzed by liquid chromatography (HPLC).
A yield of 1130 g (84% of the theoretical) of 4,4'-bis-(isopropoxycarbonylamino)-dicyclohexyl methane was determined.
LeA 19,838 Following the procedure described in Example 1, 648 g of 2,4-diaminotoluene, 637 g of urea, 153Q g of ethanol (approximately 96~) and 5.3 g of zinc octoate were reacted for 6.0 hours at 200C in the pressure apparatus described in Example 1. After cooling and venting of the apparatus, the reaction mixture was removed, filtered and analyzed by liquid chromatography (HPLC). A yield of 1070 g t76~ of the theoretical) of 2l4-bis-(ethoxycarbonylamino)-toluene was determined.
In a reaction vessel equipped with a reflux con-denser, 1 mol of aniline, 1 mol of urea and 1.4 mols of n-hexanol were rapidly heated to 140C in the presence of 1 g of zinc chloride. The reaction temperature was then generally increased to 200C over a period of 3 hours. After another 2 hours at that temperature, the reaction was complete, i.e., no more ammonia was given off. Analysis of the reaction mixture by liquid chroma-tography showed a yield of 97~, based on urea, of N-phenyl-O-hexyl urethane. The reaction mixture contained less than 1~ of carbamic acid hexyl ester.
744 g of aniline (8 mols) were mixed with 480 g of urea (8 mols), 15 ml of zinc octoate and 1200 g of cyclohexanol (12 mols) and the resulting mixture was introduced into the first three-liter vessel of a three-stage reactor. The three vessels of the reactor were heated to 170C, 200C and 205C. A mixture of 1860 g of aniline (20 mols), 1200 g of urea (20 mols), 25 ml of zinc octoate and 3 kg of cyclohexanol (30 mols), which had been heated to 100C, was pumped into the first vessel over a period of 5 hours. The apparatus was then filled and a mixture LeA 19,838 of 1660 g of aniline (20 mols), 1200 ~ of urea (20 mols), 25 ml of zinc octoate and 3 kg of cyclohexanol (30 mols) was pumped into the reactor over a period of 5 hours.
The final reaction mixture flowed continuously into a thin-layer evaporator where the cyclohexanol was removed in a water jet vacuum. 96~ of the residue left after distillation was N-phenyl-O-cyclohexyl urethane (as determlned by high pressure liquid chromatography = HPLC).
5 ml of zinc octoate were added to 170 g of isophorone diamine (1 mol), 120 g of urea (2 mols) and 250 g of cyclohexanol. The reaction mixture was heated rapidly to 135C to initiate the evolution of ammonia.
The internal temperature was increased to 205C over a period of 6 hours and kept at that level for 3 hours.
After cooling, 51 g of cyclohexanol were distilled off from the residue in a water jet vacuum, leaving a resin which was glass-like and transparent at room temperature.
IR and NR analysis indicated that the resin was almost completely the bis-urethane. 386 g of l-(cyclohexoxy-carbonylamino)-3,3,5-trimethyl-5-(cyclohexoxycarbonyl-amino methyl)-cyclohexane (91% of the theoretical) having a melting point of 159-160~ (from cleaning spirit) were produced.
122 g of 2,4-diaminotoluene (1 mol), 120 g of urea (2 mols) and 250 g of n-hexanol (2.5 mols) are admixed with 1 ml of zinc octoate. The mixture is sub-sequently heated in a reaction yessel equipped with a reflux condenser until a temperature of the mixture of 180C is reached. Subsequently 160 ml of n-hexanol are added dropwise so that the reaction temperature of 180C can be maintained. After a total reaction time of 17 hours the content of the reaction LeA 19,838 i6Z
mixture is determined by HPLC and found to correspond to 93% of the theoretical. Excess hexanol is then distilled off and the residue is recrystallized from isopropanol/
cleaning spirit. 308 g of 2,4-bis-(n-hexoxycarbonyl-amino)-toluene (-81% of theoretical yield) having a melt-ing point of from 82-83C are obtained.
EXAMPLE lla Example 11 is repeated with the only difference that O.S mol of the 2,4-diaminotoluene are replaced by 0.5 mol of 2,6-diaminotoluene. The yield of the corres-ponding urethanes was found to correspond to 91% of the theoretical yield.
324 g of 3,4-dichloroaniline (2 mols), 120 g of urea (2 mols), 300 g of cyclohexanol (3 mols) and 1 ml of zinc octoate are heated for 13 hours to reflux tempera-ture. The reaction temperature rises to 205C. After removal of excess cyclohexanol by distillation 655 g of residue are obtained which contains the urethane in an amount which corresponds to 90~ of the theoretical yield (HPLC analysis).
After recrystallization from cleaning spirit 470 g N-(3,4-dichlorophenyl)-cyclohexyl urethane (82~ of the theoretical yield) having a melting point of from 116 to 118C are obtained.
200 g of caprolactam were added to 183 g of 3-aminodibenzofuran (1 mol), 60 g of urea (1 mol), 150 g of cyclohexanol (1.5 mols) and 2 ml of zinc acetate.
The resulting mixture was heated rapidly to 200C caus-ing evolution of ammonia. After 5 hours at that tempera-ture, the reaction was complete and the excess cyclo-hexanol was distilled off. The residue was introduced into water, the insoluble fraction was filtered off, dried and recrystallized from cleaning spirit. 236 g of N-(3-dibenzofuranyl)-LeA 19,838 -16a-_-cyclohexyl urethane (76% of the theoretical) having a melting point of 13I-133C were.produced.
113 g of 4-morpholine amine (90%, 1 mol), 60 g of urea (1 mol), 150 g of cyclohexanol (1 mol) and 2 g of zinc acetate were combined and heated to 135C, initiating the evolution of ammonia. The temperature LeA 19,838 11445~2 was increased s~owly to 190~C and kept at that level for 4 hours. The excess cyclohexanol (52 g~ was removed in a water jet vacuum in a rotary evaporator and the residue was recrystallized from cleaning spirit. 166 g of N-(4-morpholinyl)-cyclohexyl urethane (73% of the theoretical) having a melting point of 150-152C were produced.
157 g of 3-aminosuifolane ~86%, 1 mol), 60 g of urea (1 mol), 150 g of cyclohexanol (1.5 mols) and 2 ml of zinc octoate were mixed in a 500 ml three-necked flask equipped with a stirrer, thermometer and reflux condenser. The resulting mixture was heated over a period of 4 hours to 190C with evolution OL
ammonia. After another 3 hours at 193C, the reaction was complete. 45 g of cyclohexanol were removed in a water jet vacuum and the residue was recrystallized from ethyl acetate. 241 g of N-(3-sulfolanyl)-cyclo-hexyl urethane (92% of the theoretical) having a melting point of 139C were produced.
324 g of benzyl alcohol (3 mols), 205 ~ of aniline (2.2 mols) and 120 g of urea (2 mols) were mixed in a one-liter flask. 1 g of zlnc octoate and 2 g of dibutyl tin dilaurate were added to the \~ resulting mixture which wa~ then rapidly heated to 135C, initiating t~e evolution of ammonia. The internal temperature was increased to 200C over a period of 3 hours and kept between 195C and 205C
for another 5 hours. On completion of the reaction, excess benzyl alcohol and aniline were distilled off in a water jet vacuum. The residue was fractionated in a high vacuum. 336 g of N-phenyl benzyl urethane (74~ of the theoretical) having a boiling point of 142-145C at 0.13 mbar were produced.
LeA 19,838 Z
2 g of zinc cyanide were added to 94 g of 2-aminopyridine (1 mol), 60 g of urea (1 mol), 150 g of cyclohexanol (1.5 mols). The resulting mixture was 5 heated to 135C, initiating the evolution of ammonia.
The temperature was increased to 200C over a period of 4 hours and left at that level for another 2 hours. 55 g of cyclohexanol were then distilled off in a water jet vacuum and the residue was recrystallized from cleaning spirit. 170 g of N-(2-pyridyl)-cyclohexyl urethane (77% of the theoretical) having a melting point of 145-147C were produced.
-2.5 ml of zinc octaate were added to 306 g of n-hexanol (3 mols), 205 g of aniline (2.2 mols) and 120 g of urea t2 mols). The resulting mixture was heated over a period of 5 hours to 200C with evolution of ammonia.
After another 3 hours at that temperature, the reaction was complete and excess cyclohexanol and aniline were removed in a water jet vacuum. The quantity of the reac-tion product was determined by HPLC to be 345 g of N-phenyl-_-hexyl urethane (87~ of the theoretical). The product crystals had a melting point of 42-43C (from cleaning spirit).
3 g of cobalt acetate were added to 127.5 g of ~-chloroaniline (1 mol), 60 g of urea (1 mol) and 140 g of cyclohexanol (1.4 mols). The reaction mixture was heated to 150C, initiating the evolution of ammonia.
The internal temperature was increased to 200C and kept at that level for 5 hours. Excess cyclohexanol was then removed by distillation and the residue was recrystal-lized from xylene. 218 g of N-t_-chlorophenyl)-cyclo-hexyl urethane (86% of the LeA 19,838 1~44562 theoretical) having a melting point of 115-116C
were produced.
E~LE 20 116 g of 1,6-diaminohexane (1 mol) r 120 g of urea (2 mols), 250 g of cyclohexanol (2.5 mols), 100 g of caprolactam and 3 ml of zinc octoate were heated to 140C, initiating the elimination of ammonia. The internal temperature was increased to 200C over a period of 4 hours and the reaction mixture was heated for another 3 hours at 205C. Cyclohexanol was then removed in a water jet vacuum and caprolactam was removed in a high vacuum. The residue wzs identified and determined by IR, NR and HPLC. 316 g of l,6-bis-(cyclohexoxycarbonylamino)-hexane (86% of the theoretical) were produced. A sample was recrystallized from cleaning spirit. The recrystallized sample had a melting point of 110-111C.
250 g of cyclohexanol ~2.5 mols), 120 g of urea (2 mols) and 3 ml of zinc octoate were heated to 140C and 118 g of propylamine (2 mols) were added slowly, dropwise, at that temperature. On completion of the addition, the internal temperature was increased to 200C and the xeaction mixture was sitrred for 1 hour at that temperature. The unreacted cyclohexanol was distilled off in a water jet vacuum and the residue was distilled in an oil pump vacuum. 292 g ~79% of the theoretical) of N-(n-propyl)-O-cyclohexyl urethane ~identified by HPLC) were produced.
198 g of 4,4'-diaminodiphenylmethane (1 mol), 120 g of urea (2 mols), 400 ml of cycloheYanol (4 mols), 3 ml of zinc octoate and 452 g of caprolactam were mixed and the resulting mixture was heated over a period of 3 hours to 210~C. After heating for 4 hours at that temperature, the evolution of ammonia LeA 19,838 ~144S62 .
was complete. The reaction mixture which had a temperature of 40C was then stirred into ice water, mixed with ethyl acetate and separated. The ethyi acetate phase was repeatedly washed with ice water, dried over sodium sulfate and concentrated. The residue was recrystallized from xylene. 415 g of 4,4'-bis-(cyclohexoxycarbonylamino)-diphenylmethane ~86% of the theoretical) having a melting point of 144C were produced.
258.3 g (2.1 mols) of 4-methoxy aniline, 120 g t2 mols) of urea and 330.4 g (2.8 mols) of glycol monobutyl ether were heated under reflux for 2 hours with 3 g of cobalt acetate. After the temperature had reached 200C, the reaction mixture was kept at that temperature for another 8 hours. After removal of the excess glycol monobutyl ether, the reaction product was dissolved in 500 ml of toluene, filtered off under suction from the insoluble residue, extracted with 1 N HCl and worked up, leaving a chromato-graphically (thin-layer chromatography) pure oil which was identified by spectroscopy as N-(4-methoxy phenyl)-O-~-n-butoxy ethyl urethane. The yield amounted to 87% of the theoretical.
_ 204.6 g (2.2 mols) of aniline, 120 g (2 mols) of urea and 354 g (3 mols) of ethylene glycol mono-butyl ether were heated under reflux with 0.8 of dibutyl tin dilaurate. After 2 hours, the temperature reached 200C and was kept at that level for another 9 hours. The solution was concentrated and the residue was treated with hot ligroin. The solution was then filtered off undér suction from the insoluble diphenyl urea and the ligroin was distilled off again, leaving a noncrystallizing oil, of which more than 95% was found by nuclear-resonance spectroscopy to LeA 19,838 consist of N-phenyl-O-~-n-butoxy ethyl urethar.e. The yield amounted to more than 90% of the tneoretical.
-204.6g(2.2 mols) of aniline, 120 g (2 mols) of urea and 366 g (3 mols) of ~-phenyl ethanol were heated with 3 g of thallium chloride. The reflux temperature rose over a period of 1.5 hours to 200C.
When the evolution of ammonia ceased, the reaction mixture was kept at 200C for another 10 hours. The yield of N-phenyl-O-~-phenyl ethyl urethane was determined by high pressure liquid chroma.ography and amounted to more than 90% of the theoretical.
. .
235.4 g (2.2 mols) of 3-methyl aniline, 120 g (2 mols) of urea and 390 g (3 mols) of 2-ethyl-1-hexanol were heated under reflux for 3 hours with 0.8 g of triethylenediamine, ammonia being given off. The temperature rose to 200C. After another 7 hours at 200C, the reaction mixture was concentrated ln vacuo.
The hot residue was mixed with 500 ml of cleaning spirit and the resulting solution filtered off under suction from the insoluble fraction. 0-2-ethyl hexyl-(l)-N-phenyl urethane was isolated from the filtrate by distillation (0.2 mbar, 147-150C) in a yield which was 85% of the theoretical yield.
354 g (1.2 mols) of ethylene glycol monobutyl ether, 120 g ~2 mols) of urea and 185.4 g (1.2 mols) of 3-aminotetramethylene sulfone were heated under reflux with 0.8 g of zinc octoate. After 3 hours, the temperature had reached 200C and was kept at that level for another 8 hours. The recyclable starting and secondary products were removed by dis-tillation at 0.6 mbar (temperature: up to 115C).
According to analysis by infrared and nuclear-resonance spectroscopy, the residue was N-(3-perhydrothiophenyl-LeA 19,838 l,l-dioxo)-O-~-_-butoxy ethyl urethane. The yield was 85% of the theoretical yield.
EXAMP~E 28 198 g (2 mols) of cyclohexyl amine, 132 g (2.2 mols) of urea and 244 g (2 mols) of ~-phenyl ethanol were heated under reflux to 200C with 0.2 g of zinc octoate. Another 122 g (1 mol) of ~-phenyl ethanol were then added and the reaction mixture was kept at 200C for 4 hours. 79% of the theoretical yield of N-cyclohexyl-O-~-phenyl ethyl urethane melting at 86 to 88C (cleaning spirit) were produced.
103 g (1 mol) of biuret, 186 g (2 mols) of aniline, 300 g (3 mols) of cyclohexanol and 0.5 g of zinc octoate were heated under reflux for 4 hours, the temperature reaching 200C. The reaction mixture was then kept at 200C for another 4 hours. The yield of O-cyclohexyl-N-phenyl urethane was determined by high pressure liquid chromatography to be 92% of the theoretical yield.
The reaction was repeated without the catalyst.
The reaction mixture was kept at 200C for a period of 20 hours. The yield of O-cyclohexyl-N-phenyl urethane was determined by high pressure liquid chromatography to be 60% of the theoretical yield.
272 g (2 mols) of 4-nitroaniline, 120 g (2 mols) of urea, 300 g (3 mols) of cyclohexanol and 0.8 g of zinc octoate were heated under reflux. After the temperature had reached 2Q0C, it was kept at that level for 7 hours.
327 g (62% of the theoretical yield) of O-cyclohexyl-n-4-nitrophenyl urethane melting at 117C were obtained by recrystallization from ethanol/water.
3-nitroaniline was reacted by the method des-cribed above, giving 370 g (70% of the theoretical) LeA 19,838 ``` 11~4S6Z
yield) of O-cyclohexyl-N-3-nitrophenyl urethane melting at 115C.
2-nitroaniline was reacted by the method described above, giving 208 g (43% of the theoretical yield) of O-cyclohexyl-N-2-nitrophenyl urethane melting at 104C.
204.6 g (2.2 mols) of aniline, 132 g (2.2 mols) of urea, 300 g (3 mols) of cyclohexanol, 0.8 g of zinc octoate and 0.2 g of tin octoate were heated under reflux. The reaction temperature was increased from 150C to 200C over a period of 2 hours. The tempera-ture was kept at 200C for another 8 hours. During the reaction, ethanol was continuously passed through the solution at a rate of 50 ml/hour and removed overhead. The urethane yields were determined by high pressure liquid chromatography. 95.4~ of the theoretical yield of O-cyclohexyl-N-phenyl urethane and 3.7% of the theoretical yield of O-ethyl-N-phenyl urethane were formed.
204.6 g (2.2 mols) of aniline, 120 g (2 mols~
of urea, 300 g (3 mols) of cyclohexanol and 0.6 g of zinc octoate were heated under reflux. The reaction temperature was raised from 150C to 200C over a period of 2 hours. When the evolution of a~monia ceased, the reaction mixture was kept at 200C with the course of the reaction being continuously monitored by high pressure li~uid chromatography. After 6 hours, the yield of O-cyclohexyl-N-phenyl urethane amounted to 97.9~ of the theoretical yield. After recry~stal-lization , 416 g (95~ of the theoretical yield) of the urethane ~Mp 80C) were obtained.
EX~MPLE 33 Phenyl carbamic acid butyl ester was produced by heating a mixture of 60.06 g (l mol) of urea, LeA 19,838 102.4 g (1.1 mol) of aniline and 0,5 resp. 2 9 Ot the catalysts mentioned below to 150C in a 500 ml three necked flask equipped with a stirrer, internal thermometer and reflux condenser. 150-200 ml of butanol were added dropwise over a period of 6 hours with stirring and further heating. The rate of addition was selected so that a reaction temperature of 175C was maintaired.
The conversion was estimated through the evolution of ammonia. The reaction mixture was worked up b,y dis-tillation of the carbamate.
The yield of N-phenyl-O-butyl urethane (HPLC Oc the reaction mixture) for catalyzed and uncatalyzed reactions were as follows:
Catalyst Yield None 140.6 g 72.8% (theoretical) 2 g of CU(oAc)2-H2o 161.0 g 83.4~ (theoretical) 0.5 g of Octasoli~en-Zn 179.2 g 92.9~ (theoretical) 186 g of aniline (2 mols), 120 g of urea (2 mols), 300 ml of cyclohexanol (3 mols) and 3 g of catalyst were boiled unaer reflux for 9 hours. The e~cess cyclo-hexanol was removed in a water jet vacuum and the yield of N-phen~-l-O-cyclohexyl urethane was determi,ned by HPLC.
The following Table illustrates the effect of the various catalysts upon the reaction described above. A noncatalyzed batch was run for purposes of comparison. Thé yields are given in terms of mol percent.
LeA 19,838 Catalyst Yield Zn-octoate 97 TlCl 95 ZnCl2 95 ZnSO4 94 5 2 94.4 Dabco 94 Co-naphthenate 94 DBU 92.5 TiCl4 92 Zn-dust 92 2-hydroxypyridine 92 K-acetate 92 BiCl3 92 BF3-etherate 91.5 Dibenzylamine 91 AlCl3 91 Zn-acetate 91 Fe-acetyl acetonate 90.5 Cu-acetate 90 Na-methylate 90 Zn~CN)2 90 ZnO 90 Sn-octoate 89.5 None 81 LeA 19,838 11~4S6Z
Example 35 A 3 l reaction vessel is equipped with a stirrer~ermometar~
reflux condenser, heatable ethanol inlet tube and a gas outlet tube. 814 g of urea, 1302 9 of aniline and 7 g of dibutyltin-oxide are heated within 1 hour to 170C.
Subsequently ethanol vapours are pumped into the reaction mixture the amount of ethanol was 400 g/h at the besinninG
of the introduction of the vapours and is continuously reduced so that a reaction temperature of 170C can be maintained. According to HPLC analysis N-phenyl-carbamic-acid ethyl ester is formed in an amount of 1779 9 (77 %of the theoretical yield) after 10 hours and in an amount of 1917 9 (83 % of the theoretical yield~ after 23 hours.
F;nally 1746 9 (76 % of the theoretical yield) of N-phenyl-carbamic acid ethyl ester can be obtained by distillatio-at 110C/0,13 mbar containing only 1,8 % by weight of N,N'-diphenylurea and 30 ppm of zinc. The distilla'ion residue (379 9) contains 21 % by weight of N-phenylcarbamic acid ethyl ester, 61 % by weight of N,N'-diphenyl urea and Z 0,85 ~ by weight of zinc.
~ ~ LeA 19 838 ~ 4S62 A 0.5 1 reaction vessel is equipped with a stirrer, dropping funnel and a reflux condenser with a gas outlet tube. The inlet tube of the dropping funnel immerses into the reaction mixture. 60.1 g of urea, 93.1 g of aniline and 0.5 g of dimethyl-tin-dichloride are heated in the reaction vessel under stirring and nitrogen to 170C Subsequently 73 g of ethanol are added at such a rate that the reaction temperature can be maintained between 170 and 175C After 10 hours the reaction is stopped by cooling to room temperature. According to HPLC analysis 140.3 g (85% of the theoretical yield) of N-phenylcarbamic acid ethyl ester have been formed.
144 g of urea, 480 g of diethylene glycol mono-methyl ether and 0.8 g of zinc octoate are heated for 1 hour to reflux temperature. At 200C 198 g of 4,4'-diamino-diphenylmethane and so much diethylene glycol dimethyl ether are added dropwise at such a rate that the temperature of the reaction mixture does not rise above 200C.
After 9 hours 4,4'-bis-[2~2'-methoxyethoxy)-ethoxy-carbonylamino]-diphenylmethane is found by HPLC
analysis in an amount which corresponds to 90% of the theoretical yield.
LeA 19,838
Claims (7)
1. A process for the production of a urethane by reacting a urea or a polyuret with a primary amine and an alcohol at a temperature in the range from 120°C
to 350°C, characterized in that the reaction is carried out in the presence of a catalyst which is an esterifica-tion catalyst for carboxylic acids.
to 350°C, characterized in that the reaction is carried out in the presence of a catalyst which is an esterifica-tion catalyst for carboxylic acids.
2. The process of Claim 1, wherein the catalyst is an inorganic or organic base which is inert under the reaction conditions.
3. The process of Claim 1, wherein the catalyst is a Lewis acid.
4. The process of Claim 1, wherein the catalyst is a transition metal salt or chelate.
5. The process of Claim 1, wherein the reaction is carried out in the presence of a polar solvent.
6. The process of Claim 1, wherein a polyuret is reacted with the primary amine and the alcohol in the presence of the catalyst.
7. The process of Claim 1, wherein urea is reacted with the primary amine and the alcohol in the presence of a catalyst.
LeA 19,838
LeA 19,838
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19792943481 DE2943481A1 (en) | 1979-10-27 | 1979-10-27 | METHOD FOR PRODUCING URETHANES AND THE USE THEREOF FOR PRODUCING ISOCYANATES |
| DEP2943481.9 | 1979-10-27 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1144562A true CA1144562A (en) | 1983-04-12 |
Family
ID=6084534
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000362772A Expired CA1144562A (en) | 1979-10-27 | 1980-10-20 | Process for the production of urethanes useful in the production of isocyanates |
Country Status (9)
| Country | Link |
|---|---|
| EP (1) | EP0027940B2 (en) |
| JP (1) | JPS57114561A (en) |
| AT (1) | ATE4640T1 (en) |
| AU (1) | AU538535B2 (en) |
| BR (1) | BR8006849A (en) |
| CA (1) | CA1144562A (en) |
| DE (2) | DE2943481A1 (en) |
| ES (1) | ES496232A0 (en) |
| ZA (1) | ZA806546B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5646328A (en) * | 1995-06-23 | 1997-07-08 | Bayer Aktiengesellschaft | Process for removing by-products from diurethanes |
| US5744633A (en) * | 1993-12-13 | 1998-04-28 | Bayer Aktiengesellschaft | Process for the production of diurethanes and their use for the production of diisocyanates |
| US6410778B2 (en) * | 1995-11-07 | 2002-06-25 | Basf Aktiengesellschaft | Method of producing organic diurethanes and/or polyurethanes and their use in the production of di and/or polyisocyanates |
| US20120010427A1 (en) * | 2009-03-26 | 2012-01-12 | Mitsui Chemicals, Inc. | Urethane compound and method for producing the same, and isocyanate and method for producing the same |
| US8742164B2 (en) | 2010-07-07 | 2014-06-03 | Mitsui Chemicals, Inc. | Method for producing toluenedicarbamate, method for producing toluenediisocyanate, and toluenedicarbamate |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3110573A1 (en) * | 1981-03-18 | 1982-10-21 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING N- AND O-SUBSTITUTED DI- AND / OR POLYURETHANES |
| DE3523692A1 (en) * | 1985-07-03 | 1987-01-08 | Basf Ag | METHOD FOR PRODUCING (OMEGA) -ISOCYANATOALKYL (METH) ACRYLATES |
| US4925971A (en) * | 1987-12-08 | 1990-05-15 | Asahi Kasei Kogyo Kabushiki Kaisha | Method for producing aliphatic o-arylurethanes |
| DE4441176A1 (en) | 1994-11-18 | 1996-05-23 | Bayer Ag | Polyisocyanates containing allophanate groups |
| WO2001047870A2 (en) * | 1999-12-27 | 2001-07-05 | Huntsman International Llc | Process for the production of aromatic polycarbamates |
| WO2010116871A1 (en) * | 2009-04-09 | 2010-10-14 | 三井化学株式会社 | Urethane compound and process for production thereof, and isocyanate and process for production thereof |
| JP5643517B2 (en) * | 2010-02-04 | 2014-12-17 | 三井化学株式会社 | Catalyst treatment method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2409712A (en) * | 1944-02-03 | 1946-10-22 | Du Pont | Chemical process and products |
| US2806051A (en) * | 1955-11-01 | 1957-09-10 | Goodrich Co B F | Method for preparing urethanes by reacting urea, amines and an alcohol |
| DE2917493A1 (en) * | 1979-04-30 | 1980-11-13 | Basf Ag | METHOD FOR PRODUCING ALIPHATIC AND CYCLOALIPHATIC DI- AND POLYURETHANES |
| DE2917569A1 (en) * | 1979-04-30 | 1980-11-13 | Basf Ag | METHOD FOR PRODUCING AROMATIC DI- AND POLYURETHANES |
-
1979
- 1979-10-27 DE DE19792943481 patent/DE2943481A1/en not_active Withdrawn
-
1980
- 1980-10-11 DE DE8080106196T patent/DE3064837D1/en not_active Expired
- 1980-10-11 EP EP80106196A patent/EP0027940B2/en not_active Expired
- 1980-10-11 AT AT80106196T patent/ATE4640T1/en not_active IP Right Cessation
- 1980-10-20 CA CA000362772A patent/CA1144562A/en not_active Expired
- 1980-10-24 ES ES496232A patent/ES496232A0/en active Granted
- 1980-10-24 BR BR8006849A patent/BR8006849A/en unknown
- 1980-10-24 ZA ZA00806546A patent/ZA806546B/en unknown
- 1980-10-25 JP JP55148903A patent/JPS57114561A/en active Granted
- 1980-10-27 AU AU63713/80A patent/AU538535B2/en not_active Ceased
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5744633A (en) * | 1993-12-13 | 1998-04-28 | Bayer Aktiengesellschaft | Process for the production of diurethanes and their use for the production of diisocyanates |
| US5646328A (en) * | 1995-06-23 | 1997-07-08 | Bayer Aktiengesellschaft | Process for removing by-products from diurethanes |
| US6410778B2 (en) * | 1995-11-07 | 2002-06-25 | Basf Aktiengesellschaft | Method of producing organic diurethanes and/or polyurethanes and their use in the production of di and/or polyisocyanates |
| US20120010427A1 (en) * | 2009-03-26 | 2012-01-12 | Mitsui Chemicals, Inc. | Urethane compound and method for producing the same, and isocyanate and method for producing the same |
| CN102348679A (en) * | 2009-03-26 | 2012-02-08 | 三井化学株式会社 | Urethane compound and process for production thereof, and isocyanate and process for production thereof |
| CN102348679B (en) * | 2009-03-26 | 2014-09-10 | 三井化学株式会社 | Urethane compound and process for production thereof, and isocyanate and process for production thereof |
| TWI466857B (en) * | 2009-03-26 | 2015-01-01 | Mitsui Chemicals Inc | A method for producing an ethylcarbamate compound, and a method for producing a isocyanate |
| US9150502B2 (en) | 2009-03-26 | 2015-10-06 | Mitsui Chemicals, Inc. | Urethane compound and method for producing the same, and isocyanate and method for producing the same |
| US8742164B2 (en) | 2010-07-07 | 2014-06-03 | Mitsui Chemicals, Inc. | Method for producing toluenedicarbamate, method for producing toluenediisocyanate, and toluenedicarbamate |
| EP2592069A4 (en) * | 2010-07-07 | 2016-05-25 | Mitsui Chemicals Inc | Method of producing toluenedicarbamate, method of producing toluenediisocyanate, and toluenedicarbamate |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0027940A1 (en) | 1981-05-06 |
| ES8106883A1 (en) | 1981-09-16 |
| ES496232A0 (en) | 1981-09-16 |
| ATE4640T1 (en) | 1983-09-15 |
| JPH0314819B2 (en) | 1991-02-27 |
| JPS57114561A (en) | 1982-07-16 |
| AU538535B2 (en) | 1984-08-16 |
| DE3064837D1 (en) | 1983-10-20 |
| ZA806546B (en) | 1981-11-25 |
| EP0027940B2 (en) | 1986-12-30 |
| BR8006849A (en) | 1981-04-28 |
| EP0027940B1 (en) | 1983-09-14 |
| DE2943481A1 (en) | 1981-05-07 |
| AU6371380A (en) | 1981-04-30 |
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